ATBECHDEDKESFRGBGRITLILUNLSEMCPTIESILTLVFIROMKCYALTRBGCZEEHUPLSK..HRIS..MTNORSMESM..................*JBDM Ver 0.1.63 (23 May 2017) - 2100000/0The file contains technical information submitted after the application was filed and not included in this specification2864320EUROPEAN PATENT SPECIFICATIONB120171115EP13728196.0201306122015012020160823enenen201261661817 P20120620US201261717117 P20121023US20171115201746201504292015182017111520174620170627C07D 403/12 20060101AFI20140116BHEP A01N 43/58 20060101ALI20140116BHEP A01N 51/00 20060101ALI20140116BHEP A01N 43/56 20060101ALI20140116BHEP A01N 47/02 20060101ALI20140116BHEP A01N 43/36 20060101ALI20140116BHEP A01N 37/46 20060101ALI20140116BHEP A01N 47/24 20060101ALI20140116BHEP A01N 43/78 20060101ALI20140116BHEP A01N 43/653 20060101ALI20140116BHEP dePESTIZIDE PYRAZOL-VERBINDUNGENenPESTICIDAL PYRAZOLE COMPOUNDSfrCOMPOSÉ DE PYRAZOLE PESTICIDESWO-A1-2010/03473717193945.720170929SÖRGEL, SebastianMarienstraße 1967063 LudwigshafenDESÄLINGER, DanielIn den Weihergärten 2067071 LudwigshafenDEDEFIEBER, ChristianVischerstrasse 367117 LimburgerhofDELANGEWALD, JürgenJoseph-Haydn-Straße 3-568165 MannheimDEGOCKEL, BirgitEschenbachstraße 4267063 LudwigshafenDEHADEN, EgonMaulbronner Hof 2467346 SpeyerDECULBERTSON, Deborah L.6400 Vintage Ridge LaneFuquay Varina, NC 27526USGUNJIMA, KoshiHeights Takara-3 205 97 Shirakawa-choToyohashi-city Aichi Prefecture 441-8021JPBASF SE101572067PF 73678 SECarl-Bosch-Strasse 3867056 Ludwigshafen am RheinDEBASF IP Association101647202BASF SE G-FLP-C00667056 LudwigshafenDEALATBEBGCHCYCZDEDKEEESFIFRGBGRHRHUIEISITLILTLULVMCMKMTNLNOPLPTRORSSESISKSMTRME20150120EP201306212320130612enWO20131898012013122720135220150429201518

The present invention relates to novel pyrazole compounds of the formula I wherein

R1
is H, C1-C2-alkyl, or C1-C2-alkoxy-C1-C2-alkyl;
R2
is CH3, CH2F, CHF2, or CF3;
R3
is a monospiro or dispiro 5- to 10-membered carbo- or heterocycle, which may contain 1 or 2 heteroatom moieties selected from N-Rc, O, and S(O)k, with k being 0 1 or 2, which monospiro or dispiro 5- to 10-membered carbo- or heterocycle is unsubstitued or may be substituted by 1, 2, 3 or 4 radicals Ra3;
Ra1 is CN, NO2, C(O)NH2, C(S)NH2, C1-C2-alkylcarbonyloxy, C1-C4-alkoxy, C1-C2-halo-alkoxy, C1-C2-alkyloxycarbonyl, or S(O)nRb;
Ra2 is halogen, or a group mentioned for Ra1;
Ra3 is halogen, C1-C2-alkyl, C1-C2-haloalkyl, C1-C2-alkoxy-C1-C2-alkyl, C1-C2-alkyliden, =O, =S, =NRb, =NORb, =NSRb, or a group mentioned for Ra1; in particular halogen, C1-C2-alkyl, C1-C2-alkoxy-C1-C2-alkyl, C1-C2-alkyliden, or a group mentioned for Ra1;
n is 0, 1, or 2;
Rb is H, C1-C2-alkyl, C1-C2-haloalkyl, C3-C6-cycloalkyl, or C1-C4-alkoxy,
Rc is H, C1-C2-alkyl, C1-C2-haloalkyl, C1-C2-alkylcarbonyl, or C1-C2-alkoxy-carbonyl;
R4
is C1-C4-alkyl or C1-C4-haloalkyl; or
R3 and R4
together with the carbon atom, to which they are attached, form a monospiro or dispiro 5 to 10-membered carbo- or heterocycle, which may contain 1 or 2 heteroatom moieties selected from N-Rc, O, and S(O)k, with k being 0, 1 or 2, which monospiro or dispiro 5 to 10-membered carbo- or heterocycle is unsubstitued or may be substituted by 1, 2, 3 or 4 radicals Ra3;
Ra3 is selected from CN, C1-C2-alkoxy, C1-C2-alkylsulfanyl, C1-C2-fluoroalkoxy, and C1-C2-fluoroalkylsulfanyl; and
R5
is H, CH3, CN, F, OCH3, SCH3, CF3, OCF3, or SCF3; and
the stereoisomers, salts, tautomers and N-oxides thereof.

Moreover, the present invention relates to

The term "invertebrate pest" (also referred to as animal pests) as used herein encompasses animal populations, such as insects, arachnids and nematodes, which may attack plants, thereby causing substantial damage to the plants attacked, as well as ectoparasites which may infest animals, in particular warm blooded animals such as e.g. mammals or birds, or other higher animals such as reptiles, amphibians or fish, thereby causing substantial damage to the animals infested.

The term "compound(s) according to the invention", or "compound(s) of formula I" or "pyrazole compound(s) A" comprises the compound(s) as defined herein as well as a stereoisomer, salt, tautomer or N-oxide thereof. The term "compound(s) of the present invention" is to be understood as equivalent to the term "compound(s) according to the invention", therefore also comprising a stereoisomer, salt, tautomer or N-oxide thereof.

The term "stereoisomers" encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis/trans isomers).

Depending on the substitution pattern, the compounds of formula I may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers. One center of chirality is the carbon atom carrying radicals R3, R4 and R5. The invention provides both the pure enantiomers or diastereomers and their mixtures and the use according to the invention of the pure enantiomers or diastereomers of the compound I or its mixtures. Suitable compounds of the formula I also include all possible geometrical stereoisomers (cis/trans isomers) and mixtures thereof.

The term "N-oxide" relates to a form of compounds I in which at least one nitrogen atom is present in oxidized form (as NO).

The compounds of the present invention may be amorphous or may exist in one ore more different crystalline states (polymorphs) which may have a different macroscopic properties such as stability or show different biological properties such as activities. The present invention includes both amorphous and crystalline compounds of the formula I, mixtures of different crystalline states of the respective compound I, as well as amorphous or crystalline salts thereof.

Salts of the compounds of the formula I are preferably agriculturally and veterinarily acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality or by reacting an acidic compound of formula I with a suitable base.

Suitable agriculturally acceptable salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention. Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH4+) and substituted ammonium in which one to four of the hydrogen atoms are replaced by C1-C4-alkyl, C1-C4-hydroxyalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, hydroxy-C1-C4-alkoxy-C1-C4-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethylammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzl-triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium.

Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting a compound of formulae I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

By the term "veterinarily acceptable salts" is meant salts of those cations or anions which are known and accepted in the art for the formation of salts for veterinary use. Suitable acid addition salts, e.g. formed by compounds of formula I containing a basic nitrogen atom, e.g. an amino group, include salts with inorganic acids, for example hydrochlorids, sulphates, phosphates, and nitrates and salts of organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.

The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix Cn-Cm indicates in each case the possible number of carbon atoms in the group.

The term "halogen" denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine.

The term "heterocyclyl" includes in general 3- to 6-membered, in particular 5- or 6-membered monocyclic heterocyclic non-aromatic radicals. The heterocyclic non-aromatic radicals usually comprise 1 or 2 heteroatoms selected from N, O and S as ring members, where S-atoms as ring members may be present as S, SO or SO2.

The term "monospiro 5- to 10-membered carbocycle" refers to a bicyclic ring system of 5-, 6-, 7-, 8-, 9- or 10 carbon atoms having one atom in common (spiroatom). Examples are spiro[2.2]pentyl, spiro[2.3]hexyl, spiro[2.4]heptyl, spiro[3.4]octyl, spiro[3.5]nonyl, spiro[3.6]deyl, spiro[4.4]nonyl and spiro[4.5]decyl.

The term "dispiro 5- to 10-membered carbocycle" refers to a tricyclic ring system of 5-, 6-, 7-, 8-, 9- or 10 carbon atoms having 2 spiroatoms. Examples are dispiro[2.0.2.1]heptyl, dispiro[2.0.3.1]octyl, dispiro[3.0.3.1]nonyl, dispiro[2.0.4.1]nonyl, dispiro[2.1.2.1]octyl, dispiro[2.1.3.1]nonyl and dispiro[3.1.3.1]decyl.

The term "monospiro or dispiro 5- to 10-membered heterocycle" refers to a bicyclic or tricyclic ring system of 5-, 6-, 7-, 8-, 9- or 10 ring atoms which has one or two spiroatoms. The heterocyclic ring system usually comprise 1 or 2 heteroatoms selected from N, O and S as ring members, where S-atoms as ring members may be present as S, SO or SO2. Examples are:

In the above structures # denotes the attachment point to the remainder of the molecule. The attachment point is not restricted to the ring on which is shown, but can be on either of the spiro rings, and may be on a carbon or on a nitrogen ring atom. If the rings carry one or more substituents, these may be bound to carbon and/or to nitrogen ring atoms.

Particularly suitable are compounds of the formula I in which R1 is H, C1-C2-alkyl, or C1-C2-alkoxymethyl. More preferably, R1 is CH3, or C2H5.

Particularly suitable are compounds of the formula I in which R2 is CH3, CHF2, or CF3, especially CH3.

Particularly suitable for the invention are compounds of the formula I in which R3 is a 5-, 6-, 7-, 8-, 9-, or 10-membered monospiro- or dispirocarbocycle which is unsubstituted or substituted by 1 or 2 radicals Ra3. Ra3, if present, is preferably selected from CN, C1-C2-haloalkyl, C1-C2-alkylidene, and C1-C2-alkoxy-C1-C2-alkyl. In another embodiment Ra3 is haloalkyl, preferably CHF2, or CF3, preferred CF3. Substituents Ra3 are preferably in 1- or 4-position, if the carbocycle is monosubstituted and in 4,4-position, if the carbocycle is disubstituted. More preferably, R3 is spiro[2.2]pentyl, which is unsubstituted or carries one or two radicals Ra3 or 7-dispiro[2.0.1.2]-heptyl which is unsubstituted or carries a radical Ra3. R3 is even more preferably selected from the group consisting of spiro[2.2]pentyl, 2-methylene-spiro[2.2]pentyl, 1-CN-spiro[2.2]pentyl, 1-CF3-spiro[2.2]pentyl, 4-CH3-spiro[2.2]pentyl, 4,4-(CH3)2-spiro[2.2]pentyl, 4-(CH2OCH3)-spiro[2.2]pentyl, 4-CF3-spiro[2.2]pentyl, and 7-dispiro[2.0.2.1]-heptyl.

Preferred meanings of the variable R3 are selected from the radicals R3.1, R3.2, R3.3, R3.4, R3.5, R3.6, R3.7, R3.8, and R3.9 shown below: # denotes the point of attachment to the remainder of the molecule.

Particularly suitable for the invention are compounds of the formula I in which R4 is in particular C1-C4-fluoroalkyl. More preferably, R4 is CH3, C2H5, CHF2 or CF3, especially CH3.

Preferred meanings of the variable R3 and R4 together with the carbon atom, to which they are attached, form a monospiro or dispiro carbocycle, which is unsubstituted or substituted are selected from the radicals R3.54, R3.55, R3.56, R3.57, R3.58, R3.59, R3.60, R3.61 and R3.62 shown below: where # denotes the point of attachment to the remainder of the molecule.
R5 is preferably H, or CN, especially H.

The examples of compounds of formula I of table I include their tautomers, racemic mixtures, individual pure enantiomers and diasteroemers and their optically active mixtures.

In compounds I, R1 is in particular CH3 or C2H5. R2 is preferably CH3, CHF2, or CF3.

In compounds I, the variable R3 is preferably a monospiro or dispiro 5-, 6-, 7-, 8-, 9- or 10-membered carbocycle which is unsubstituted or substituted by 1 or 2 radicals Ra3. Ra3, if present, is preferably selected from cyano, C1-C2-haloalkyl, C1-C2-alkylidene and C1-C2-alkoxy-C1-C2-alkyl. Substituents Ra3 are preferably in 1- or 4-position, if the carbocycle is monosubstituted and in 4,4-position, if the carbocycle is disubstituted. More preferably, R3 is spiro[2.2]pentyl, which is unsubstituted or carries one or two radicals Ra3 or 7-dispiro[2.0.1.2]-heptyl which is unsubstituted or carries a radical Ra3. R3 is even more preferably selected from the group consisting of spiro[2.2]pentyl (R3.1), 2-methylene-spiro[2.2]pentyl (R3.2), 1-CN-spiro[2.2]pentyl (R3.3), 1-(CF3)-spiro[2.2]pentyl (R3.4), 4,4-(CH3)2-spiro[2.2]pentyl (R3.5), 4-CH3-spiro[2.2]pentyl (R3.6), 4-(CF3)-spiro[2.2]pentyl (R3.7), 4-(CH2OCH3)-spiro[2.2]pentyl (R3.8), and 7-dispiro[2.0.2.1]-heptyl (R3.9).

In compounds I, the variable R4 is preferably CH3, C2H5, CHF2, or CF3.

Specific compounds of this embodiment are compiled in table V below. Table V No. R1 R2 R3 R4 R5 V-1 H CH3 spiro[2.2]pentyl CH3 H V-2 CH3 CH3 spiro[2.2]pentyl CH3 H V-3 CH2CH3 CH3 spiro[2.2]pentyl CH3 H V-4 H CH3 1-CN-spiro[2.2]pentyl CH3 H V-5 CH3 CH3 1-CN-spiro[2.2]pentyl CH3 H V-6 CH2CH3 CH3 1-CN-spiro[2.2]pentyl CH3 H V-7 H CH3 4,4-(CH3)2-spiro[2.2]pentyl CH3 H V-8 CH3 CH3 4,4-(CH3)2-spiro[2.2]pentyl CH3 H V-9 CH2CH3 CH3 4,4-(CH3)2-spiro[2.2]pentyl CH3 H V-10 H CH3 4-(CH2OCH3)-spiro[2.2]pentyl CH3 H V-11 CH3 CH3 4-(CH2OCH3)-spiro[2.2]pentyl CH3 H V-12 CH2CH3 CH3 4-(CH2OCH3)-spiro[2.2]pentyl CH3 H V-13 H CH3 1-[C(=O)NH2]-spiro[2.2]pentyl CH3 H V-14 CH3 CH3 1-[C(=O)NH2]-spiro[2.2]pentyl CH3 H V-15 CH2CH3 CH3 1-[C(=O)NH2]-spiro[2.2]pentyl CH3 H

The compounds according to the invention can be prepared analogously to the synthesis routes described in WO 2009/027393 and WO 2010/034737 according to standard processes of organic chemistry, for example according to the following synthesis route:

In scheme 1, R1, R2, R3, R4 and R5 are as defined above. Activated pyrazole carboxylic acid derivatives II are preferably halides, activated esters, anhydrides, azides, for example chlorides, fluorides, bromides, para-nitrophenyl esters, pentafluorophenyl esters, N-hydroxysuccinimides, hydroxybenzotriazol-1-yl esters. For example, X is a suitable leaving group such as halogen, N3, p-nitrophenoxy or pentafluorophenoxy and the like.

Compounds of formula I, wherein R1 is different from hydrogen can also be prepared by alkylating the amides I, in which R1 is hydrogen, using suitable alkylating agents in the presence of bases. The alkylation can be effected under standard conditions known from literature.

Formula I compounds may be present in three isomeric forms:

For reasons of clarity it is referred to isomer T-A only throughout the specification, but its description embraces disclosure of the other isomers as well.

Isomer T-C can be obtained by alkylation of compounds I, wherein R1 is hydrogen. The reaction can be performed by analogy to known N-alkylation of pyridazines. N-alkylation of pyridazines is known in literature and can be found in e.g.: J. Chem. Soc., Perkin Trans. Vol. 1, p. 401 (1988), and J. Org. Chem. Vol. 46, p. 2467 (1981).

The compounds II and III are known in the art or are commercially available or can be prepared by methods known from the literature (cf. WO 05/040169; WO 08/074824; Journal of Fluorine chemistry 132(11), p.995 (2011)).

N-oxides of the compounds of formula I, can be prepared by oxidation of compounds I according to standard methods of preparing heteroaromatic N-oxides, e.g. by the method described in Journal of Organometallic Chemistry 1989, 370, 17-31.

If individual compounds cannot be prepared via the above-described routes, they can be prepared by derivatization of other compounds I or by customary modifications of the synthesis routes described. For example, in individual cases, certain compounds I can advantageously be prepared from other compounds I by ester hydrolysis, amidation, esterification, ether cleavage, olefination, reduction, oxidation and the like.

The reaction mixtures are worked up in the customary manner, for example by mixing with water, separating the phases, and, if appropriate, purifying the crude products by chromatography, for example on alumina or on silica gel. Some of the intermediates and end products may be obtained in the form of colorless or pale brown viscous oils which are freed or purified from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, they may be purified by recrystallization or trituration.

The inventive compounds have excellent activity against a broad spectrum of animal pests. They are in particular suitable for efficiently controlling invertebrate pests. Particularier, they are suitable for efficiently controlling arthropodal pests such as arachnids, myriapedes and insects as well as nematodes.

In particular, they are suitable for controlling insect pests, such as insects from the order of
lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis;
beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabrotica longicornis, Diabrotica semipunctata, Diabrotica 12-punctata Diabrotica speciosa, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria;
flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antigua, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis eguestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia titillanus, Mayetiola destructor, Musca autumnalis, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora discolour, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis, Sarcophaga spp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea, and Tipula paludosa;
thrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips ssp., Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Reticulitermes santonensis, Reticulitermes grassei, Termes natalensis, and Coptotermes formosanus;
cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis;
bugs, aphids, leafhoppers, whiteflies, scale insects, cicadas (Hemiptera), e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis, Thyanta perditor, Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Bre vicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzus persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasono via ribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion a venae, Trialeurodes vaporariorum, Toxoptera aurantiiand, Viteus vitifolii, Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., and Arilus critatus;
ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampa minuta, Hoplocampa testudinea, Lasius niger, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidole megacephala, Dasymutilla occidentalis, Bombus spp., Vespula squamosa, Paravespula vulgaris, Paravespula pennsylvanica, Paravespula germanica, Dolichovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepithema humile;
crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminifera, and Locustana pardalina;
arachnoidea, such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Ambryomma maculatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Ornithodorus moubata, Ornithodorus hermsi, Ornithodorus turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes o vis, Rhipicephalus sanguineus, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and Oligonychus pratensis; Araneida, e.g. Latrodectus mactans, and Loxosceles reclusa;
fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
silverfish, firebrat (Thysanura), e.g. Lepisma saccharina and Thermobia domestica,
centipedes (Chilopoda), e.g. Scutigera coleoptrata,
millipedes (Diplopoda), e.g. Narceus spp.,
earwigs (Dermaptera), e.g. forficula auricularia,
lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus.

Collembola (springtails), e.g. Onychiurus ssp..

They are also suitable for controlling nematodes : plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; Awl nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongates and other Longidorus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species.

They are also useful for controlling arachnids (Arachnoidea), such as acarians (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis.

The formulations are prepared in a known manner (see e.g. for review US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and et seq. WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701, US 5,208,030, GB 2,095,558, US 3,299,566, Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989 and Mollet, H., Grubemann, A., Formulation tech-nology, Wiley VCH Verlag GmbH, Weinheim (Germany), 2001, 2. D. A. Knowles, Chemistry and Technology of Agrochemical Formulations, Kluwer Academic Publishers, Dordrecht, 1998 (ISBN 0-7514-0443-8), for example by extending the active com-pound with auxiliaries suitable for the formulation of agrochemicals, such as solvents and/or carriers, if desired emulsifiers, surfactants and dispersants, preservatives, antifoaming agents, anti-freezing agents, for seed treatment formulation also optionally gelling agents.

Examples of suitable solvents are water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP(N-methyl-pyrrolidone), NOP (N-octyl-pyrrolidone), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used.

Suitable emulsifiers are nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates).

Examples of dispersants are lignin-sulfite waste liquors and methylcellulose.

Suitable surfactants used are alkali metal, alkaline earth metal and ammonium salts of ligno-sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalene-sulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ether, tri-stearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxy-propyl-ene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite waste liquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, highly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water.

Also anti-freezing agents such as glycerin, ethylene glycol, propylene glycol and bacte-ricides such as can be added to the formulation.

Suitable antifoaming agents are for example antifoaming agents based on silicon or magnesium stearate.

A suitable preservative is e.g. dichlorophen.

An example of a gelling agent is carrageen (Satiagel®)

Powders, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers.

Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, cal-cium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertiliz-ers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium ni-trate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.

In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compounds. In this case, the active compounds are employed in a purity of from 90% to 100% by weight, preferably 95% to 100% by weight (according to NMR spectrum).

For seed treatment purposes, respective formulations can be diluted 2-10 fold leading to concentrations in the ready to use preparations of 0.01 to 60% by weight active compounds by weight, preferably 0.1 to 40% by weight.

The term "seed treatment" comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.

The mixtures of the present invention can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; they are intended to ensure in each case the finest possible distribution of the active compounds according to the invention.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. However, it is also possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1 % per weight.

The active compound(s) may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active compound, or even to apply the active compound without additives.

The following are examples of formulations:

  1. 1. Products for dilution with water for foliar applications. For seed treatment purposes, such products may be applied to the seed diluted or undiluted.
    1. A) Water-soluble concentrates (SL, LS)
      10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active compound(s) dissolve(s) upon dilution with water, whereby a formulation with 10 % (w/w) of active compound(s) is obtained.
    2. B) Dispersible concentrates (DC)
      20 parts by weight of the active compound(s) are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvi-nylpyrrolidone. Dilution with water gives a dispersion, whereby a formulation with 20% (w/w) of active compound(s) is obtained.
    3. C) Emulsifiable concentrates (EC)
      15 parts by weight of the active compound(s) are dissolved in 7 parts by weight of xy-lene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion, whereby a formu-lation with 15% (w/w) of active compound(s) is obtained.
    4. D) Emulsions (EW, EO, ES)
      25 parts by weight of the active compound(s) are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of wa-ter by means of an emulsifier machine (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion, whereby a formulation with 25% (w/w) of active compound(s) is obtained.
    5. E) Suspensions (SC, OD, FS)
      In an agitated ball mill, 20 parts by weight of the active compound(s) are comminuted with addition of 10 parts by weight of dispersants, wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound(s) suspension. Dilution with water gives a stable suspension of the active compound(s), whereby a formulation with 20% (w/w) of active compound(s) is obtained.
    6. F) Water-dispersible granules and water-soluble granules (WG, SG)
      50 parts by weight of the active compound(s) are ground finely with addition of 50 parts by weight of dispersants and wetters and made as water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluid-ized bed). Dilution with water gives a stable dispersion or solution of the active com-pound(s), whereby a formulation with 50% (w/w) of active compound(s) is obtained.
    7. G) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS)
      75 parts by weight of the active compound(s) are ground in a rotor-stator mill with addi-tion of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound(s), whereby a formulation with 75% (w/w) of active compound(s) is obtained.
    8. H) Gel-Formulation (GF)
      In an agitated ball mill, 20 parts by weight of the active compound(s) are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of gelling agent wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound(s) suspension. Dilution with water gives a stable suspension of the active compound(s), whereby a formulation with 20% (w/w) of active compound(s) is obtained.
  2. 2. Products to be applied undiluted for foliar applications. For seed treatment pur-poses, such products may be applied to the seed diluted or undiluted.
    • I) Dustable powders (DP, DS)
      5 parts by weight of the active compound(s) are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable product having 5% (w/w) of active compound(s).
    • J) Granules (GR, FG, GG, MG)
      0.5 part by weight of the active compound(s) is ground finely and associated with 95.5 parts by weight of carriers, whereby a formulation with 0.5% (w/w) of active com-pound(s) is obtained. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted for foliar use.
    • K) ULV solutions (UL)
      10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product having 10% (w/w) of active compound(s), which is applied undiluted for foliar use.

Various types of oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active ingredients, if appropriate just immediately prior to use (tank mix). These agents usually are admixed with the agents according to the invention in a weight ratio of 1:10 to 10:1.

The compounds of the present invention, the compositions comprising them are employed as such or in form of compositions by treating the insects, or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from insecticidal attack with a pesticidally effective amount of the active compounds. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the insects.

The present invention also includes a method of combating animal pests which comprises contacting the fungi and/or animal pests, their habit, breeding ground, food supply, cultivated plants, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of a mixture according to the present invention or a compound of the invention. The compounds of the present invention, compositions comprising them, the inventive mixtures or compositions of these mixtures can also be employed for protecting plants from attack or infestation by invertebrate pests such as insects, acarids or nematodes comprising contacting a plant, or soil or water in which the plant is growing.

The compounds according to the present invention are effective through both contact and ingestion.

According to a preferred embodiment of the invention, the compounds according to the present invention are employed via soil application. Soil application is especially favorable for use against ants, termites, crickets, or cockroaches.

According to another preferred embodiment of the invention, for use against non crop pests such as ants, termites, wasps, flies, mosquitoes, crickets, locusts, or cockroaches the compounds of the present invention are prepared into a bait preparation. The compounds according to the invention may also be applied against said non-crop pests.

Compositions comprising an inventive compound of the formula I may further contain other active ingredients than those listed above. Compositions of this invention may further contain other active ingredients than those listed above. For example fungicides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators and safeners. These additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.

"Locus" means a plant, seed, soil, area, material or environment in which a pest is growing or may grow.

The inventive compounds I can also be employed for protecting plants from attack or infestation by invertrebrate pests such as insects, acarids or nematodes comprising contacting a plant, or soil or water in which the plant is growing.

The inventive compounds are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part) and through trophallaxis and transfer.

Preferred application methods are into water bodies, via soil, cracks and crevices, pastures, manure piles, sewers, into water, on floor, wall, or by perimeter spray application and bait.

According to another preferred embodiment of the invention, for use against non crop pests such as ants, termites, wasps, flies, mosquitoes, crickets, locusts, or cockroaches the inventive mixtures are prepared into a bait preparation.

The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). The bait employed in the composition is a product which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitoes, crickets etc. or cockroaches to eat it. This attractant may be chosen from feeding stimulants or para and / or sex pheromones readily known in the art.

Methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with the inventive mixtures and their respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like. Insecticidal compositions for application to fibers, fabric, knitgoods, non-wovens, netting material or foils and tarpaulins preferably comprise a composition including the inventive mixtures, optionally a repellent and at least one binder.

The compounds according to the invention, and the compositions comprising them can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities).

In the case of soil treatment or of application to the pests dwelling place or nest, the quantity of active ingredient(s) ranges from 0.0001 to 500 g per 100 m2, preferably from 0.001 to 20 g per 100 m2.

Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound(s) per m2 treated material, desirably from 0.1 g to 50 g per m2.

Insecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and / or insecticide.

For use in bait compositions, the typical content of active ingredient(s) is from 0.0001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compound. The composition used may also comprise other additives such as a solvent of the active material, a flavoring agent, a preserving agent, a dye or a bitter agent. Its attractiveness may also be enhanced by a special color, shape or texture.

For use in treating crop plants, the rate of application of the mixture of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.

In the context of the present invention, the term plant refers to an entire plant, a part of the plant or the plant propagation material.

The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants. Seedlings and young plants, which are to be transplanted after germination or after emergence from soil, may also be mentioned. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.

The term "cultivated plants" is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering. Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.

The protection of the resulting plant's roots and shoots is preferred.

More preferred is the protection of resulting plant's shoots from piercing and sucking insects.

The present invention therefore comprises a method for the protection of seeds from insects, in particular from soil insects and of the seedlings' roots and shoots from insects, in particular from soil and foliar insects, said method comprising contacting the seeds before sowing and/or after pregermination with mixtures according to the present invention. Particularly preferred is a method, wherein the plant's roots and shoots are protected, more preferably a method, wherein the plants shoots are protected form piercing and sucking insects, most preferably a method, wherein the plants shoots are protected from aphids.

The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.

The term seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.

The present invention also comprises seeds coated with or containing the active compound(s). The term "coated with and/or containing" generally signifies that the active ingredient(s) are for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application. When the said propagation products are (re)planted, it may absorb the active ingredient.

Suitable seeds are seeds of cereals, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.

In addition, the mixtures according to the invention may also be used for the treatment seeds from plants, which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods.

In the treatment of seeds the corresponding formulations are applied by treating the seeds with an effective amount of the mixture according to the present invention. Herein, the application rates of the active compound(s) are generally from 0,1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 2,5 kg per 100 kg of seed. For specific crops such as lettuce the rate can be higher.

Compositions, which are especially useful for seed treatment are e.g.:

Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter

In a preferred embodiment a FS formulation is used for seed treatment. Typcially, a FS formulation may comprise 1-800 g/l of active ingredient(s), 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.

An object of the present invention is therfore also to provide new methods to control parasites in and on animals. Another object of the invention is to provide safer pesticides for animals. Another object of the invention is further to provide pesticides for animals that may be used in lower doses than existing pesticides. And another object of the invention is to provide pesticides for animals, which provide a long residual control of the parasites.

The invention also relates to compositions containing a parasiticidally effective amount of compounds of formula I or the enantiomers or veterinarily acceptable salts thereof and an acceptable carrier, for combating parasites in and on animals.

The present invention also provides a method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of mixture of the present invention or a composition comprising it or the inventive compound.

The invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises a parasiticidally effective amount of a mixture of the present invention or a composition comprising it or a compound according to the invention.

Activity of compounds against agricultural pests does not suggest their suitability for control of endo- and ectoparasites in and on animals which requires, for example, low, non-emetic dosages in the case of oral application, metabolic compatibility with the animal, low toxicity, and a safe handling.

The present invention is especially useful for combating parasites of the following orders and species, respectively:

The compounds according to the invention, compositions containing them are particularly useful for the control of pests from the orders Diptera, Siphonaptera and Ixodida.

Moreover, the use of compounds according to the invention, and compositions containing them for combating mosquitoes is especially preferred.

The use of compounds according to the invention, and compositions containing them for combating flies is a further preferred embodiment of the present invention.

Furthermore, the use of the compounds according to the invention, and compositions containing them for combating fleas is especially preferred.

The use of compounds according to the invention, and compositions containing them for combating ticks is a further preferred embodiment of the present invention.

Administration can be carried out both prophylactically and therapeutically.

Administration of the active compound(s) is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally.

For oral administration to warm-blooded animals, the compound according to the invention, mixtures of the present invention may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. In addition, the mixtures of the present invention may be administered to the animals in their drinking water. For oral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula I compound, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.

Alternatively, the compounds of the invention may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The formula I compounds may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. In addition the formula I compound may be transdermally administered to animals. For parenteral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the active compounds.

The compounds according to the invention may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or water-in-oil emulsions. For topical application, dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the active compounds. In addition, the active compound mixtures may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.

Suitable preparations are:

Compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and optionally adding further ingredients such as acids, bases, buffer salts, preservatives, and solubilizers. The solutions are filtered and filled sterile.

Suitable solvents are physiologically tolerable solvents such as water, alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycols, N-methyl-pyrrolidone, 2-pyrrolidone, and mixtures thereof.

The active compounds can optionally be dissolved in physiologically tolerable vegetable or synthetic oils which are suitable for injection.

Suitable solubilizers are solvents which promote the dissolution of the active compound in the main solvent or prevent its precipitation. Examples are polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan ester.

Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid esters, and n-butanol.

Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the use concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being necessary.

Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on. Solutions for use on the skin are prepared according to the state of the art and according to what is described above for injection solutions, sterile procedures not being necessary.

Further suitable solvents are polypropylene glycol, phenyl ethanol, phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate, ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether, ketons such as acetone, methylethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylformamide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof.

It may be advantageous to add thickeners during preparation. Suitable thickeners are inorganic thickeners such as bentonites, colloidal silicic acid, aluminium monostearate, organic thickeners such as cellulose derivatives, polyvinyl alcohols and their copolymers, acrylates and methacrylates.

Gels are applied to or spread on the skin or introduced into body cavities. Gels are prepared by treating solutions which have been prepared as described in the case of the injection solutions with sufficient thickener that a clear material having an ointment-like consistency results. The thickeners employed are the thickeners given above.

Pour-on formulations are poured or sprayed onto limited areas of the skin, the active compound penetrating the skin and acting systemically.

Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in suitable skin-compatible solvents or solvent mixtures. If appropriate, other auxiliaries such as colorants, bioabsorption-promoting substances, antioxidants, light stabilizers, adhesives are added.

Suitable solvents which are: water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyethanol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as alkylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, diethylene glycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone, cyclic carbonates such as propylene carbonate, ethylene carbonate, aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, N-alkylpyrrolidones such as methylpyrrolidone, N-butylpyrrolidone or N-octylpyrrolidone, N-methylpyrrolidone, 2-pyrrolidone, 2,2-dimethyl-4-oxy-methylene-1,3-dioxolane and glycerol formal.

Suitable colorants are all colorants permitted for use on animals and which can be dissolved or suspended.

Suitable absorption-promoting substances are, for example, DMSO, spreading oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils and copolymers thereof with polyethers, fatty acid esters, triglycerides, fatty alcohols.

Suitable antioxidants are sulfites or metabisulfites such as potassium metabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole, tocopherol.

Suitable light stabilizers are, for example, novantisolic acid.

Suitable adhesives are, for example, cellulose derivatives, starch derivatives, polyacrylates, natural polymers such as alginates, gelatin.

Emulsions can be administered orally, dermally or as injections.

Emulsions are either of the water-in-oil type or of the oil-in-water type.

They are prepared by dissolving the active compound either in the hydrophobic or in the hydrophilic phase and homogenizing this with the solvent of the other phase with the aid of suitable emulsifiers and, if appropriate, other auxiliaries such as colorants, absorption-promoting substances, preservatives, antioxidants, light stabilizers, viscosity-enhancing substances.

Suitable hydrophobic phases (oils) are:

Suitable hydrophilic phases are: water, alcohols such as propylene glycol, glycerol, sorbitol and mixtures thereof.

Suitable emulsifiers are:

Suitable further auxiliaries are: substances which enhance the viscosity and stabilize the emulsion, such as carboxymethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, waxes, colloidal silicic acid or mixtures of the substances mentioned.

Suspensions can be administered orally or topically/dermally. They are prepared by suspending the active compound in a suspending agent, if appropriate with addition of other auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxidants, light stabilizers.

Liquid suspending agents are all homogeneous solvents and solvent mixtures.

Suitable wetting agents (dispersants) are the emulsifiers given above.

Other auxiliaries which may be mentioned are those given above.

Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions described above only by their higher viscosity.

For the production of solid preparations, the active compound(s) is mixed with suitable excipients, if appropriate with addition of auxiliaries, and brought into the desired form.

Suitable excipients are all physiologically tolerable solid inert substances. Those used are inorganic and organic substances. Inorganic substances are, for example, sodium chloride, carbonates such as calcium carbonate, hydrogencarbonates, aluminium oxides, titanium oxide, silicic acids, argillaceous earths, precipitated or colloidal silica, or phosphates. Organic substances are, for example, sugar, cellulose, foodstuffs and feeds such as milk powder, animal meal, grain meals and shreds, starches.

Suitable auxiliaries are preservatives, antioxidants, and/or colorants which have been mentioned above.

Other suitable auxiliaries are lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose.

In general, "parasiticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The parasiticidally effective amount can vary for the various compounds/compositions used in the invention. A parasiticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired parasiticidal effect and duration, target species, mode of application, and the like.

The compositions which can be used in the invention can comprise generally from about 0.001 to 95 wt% of the active compounds of the present invention.

Generally it is favorable to apply the active compounds of the invention in total amounts of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50 mg/kg per day.

Ready-to-use preparations contain the active compounds of the invention acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80 per cent by weight, preferably from 0.1 to 65 per cent by weight, more preferably from 1 to 50 per cent by weight, most preferably from 5 to 40 per cent by weight.

Preparations which are diluted before use contain the active compounds of the mixtures of the present invention acting against ectoparasites in concentrations of 0.5 to 90 per cent by weight, preferably of 1 to 50 per cent by weight.

Furthermore, the preparations comprise the active compounds of the invention against endoparasites in concentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to 0.9 per cent by weight, very particularly preferably of 0.005 to 0.25 per cent by weight.

In a further preferred embodiment, the topical application is conducted in the form of compound-containing shaped articles such as collars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.

Generally it is favorable to apply solid formulations which release the active compounds of the invention in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks.

For the preparation of the shaped articles, thermoplastic and flexible plastics as well as elastomers and thermoplastic elastomers are used. Suitable plastics and elastomers are polyvinyl resins, polyurethane, polyacrylate, epoxy resins, cellulose, cellulose derivatives, polyamides and polyester which are sufficiently compatible with the compounds of formula I. A detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in WO 03/086075.

Examples

The present invention is now illustrated in further details by the following examples, without imposing any limitation thereto.

Example 1: Preparation of N,5-dimethyl-N-pyridazin-4-yl-1-(1-spiro[2.2]pentan-5-ylethyl)pyrazole-4-carboxamide [I-2]

A solution of 594 mg 5-methyl-1-(1-spiro[2.2]pentan-5-ylethyl)pyrazole-4-carbonyl chloride in 5 mL THF was added dropwise to a solution of 271 mg N-methylpyridazin-4-amine and 315 mg triethylamine in 30 mL THF at 0°C. The mixture was stirred at 20-25°C for about 20 h, the solvent was evaporated and the residue was diluted with 70 mL dichloromethane, washed with 2 × 10 mL water, dried over MgSO4 and evaporated. Purification by flash chromatography (CH2Cl2/MeOH) gave 522mg of the title compound. HPLC-MS: RT 0.842 min, m/z [MH]+ 312.2

Compounds can in general be characterized e.g. by coupled High Performance Liquid Chromatography / mass spectrometry (HPLC/MS), by 1H-NMR and/or by their melting points. Analytical HPLC column: Phenomenex Kinetex 1.7 µm XB-C18 100A; 50 x 2.1 mm; mobile phase: A: water + 0.1% trifluoroacetic acid (TFA); B: acetonitrile + 0.1% TFA; gradient: 5-100% B in 1.50 minutes; 100% B 0.20 min; flow: 0.8-1.0mL/min in 1.50 minutes at 60°C.

Further compounds examples of the present invention were prepared by analogy to the above described synthetic methods and the hereunder table illustrates, without imposing any limitation thereto, compounds examples of formula I including their corresponding characterization data:
SP1 and SP2 have the following meaning in the herunder Table: wherein # denotes the bond to the skeleton of formula (I) Table I - Compounds of formula I numbered C-1 to C-15 and wherein R<sup>2</sup> is CH<sub>3</sub> and R<sup>5</sup> is H: No. R1 R3 R4 Physical data (HPLC-MS) RT [min] m/z [MH]+ C-1 H SP1 0.738 344.2 C-2 CH3 SP1 0.728 358.3 C-3 CH2CH3 SP1 0.798 372.2 C-4 CH3 SP2 0.715 330.2 C-5 CH2CH3 SP2 0.747 344.2 C-6 H SP2 0.705 316.1 C-7 H spiro[2.2]pentan-5-yl CH3 0.839 298.2 C-8 CH3 spiro[2.2]pentan-5-yl CH3 0.842 312.2 C-9 CH3 5-cyanospiro[2.2]pentan-5-yl CH3 0.727 337.2 C-10 H 5-cyanospiro[2.2]pentan-5-yl CH3 0.726 323.2 C-11 CH2CH3 5-cyanospiro[2.2]pentan-5-yl CH3 0.781 351.2 C-12 CH2CH3 spiro[2.2]pentan-5-yl CH3 0.924 326.2 C-13 H 2-(methoxymethyl)spiro[2.2]pentan-5-yl CH3 0.809 342.4 C-14 CH3 2-(methoxymethyl)spiro[2.2]pentan-5-yl CH3 0.819 356.2 C-15 CH2CH3 2-(methoxymethyl)spiro[2.2]pentan-5-yl CH3 0.861 370.2

The following tests can demonstrate the control efficacy of compounds of this invention on specific pests. However, the pest control protection afforded by the compounds, mixtures or compositions is not limited to these species. In certain instances, combinations of a compound of this invention with other invertebrate pest control compounds or agents are found to exhibit synergistic effects against certain important invertebrate pests.

B.1 Cowpea aphid (Aphis craccivora)

The active compounds were formulated in 50:50 (vol:vol) acetone:water. The test solution was prepared at the day of use. Potted cowpea plants colonized with 100 - 150 aphids of various stages were sprayed after the pest population had been recorded. Population reduction was assessed after 24, 72, and 120 hours.

In this test, the compounds C-1, C-2, C-3, C-4, C-5, C-6, C-7, C-8, C-9, C-10, C-11, and C-12 respectively at 500 ppm showed at least 75% mortality in comparison with untreated controls.

B.2 Cotton aphid (Aphis gossypii, mixed life stages)

The active compounds were formulated in cyclohexanone as a 10,0000 ppm solution supplied in 1.3 ml ABgene® tubes. These tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone: 50% water (v/v). A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v).

Cotton plants at the cotyledon stage were infested with aphids prior to treatment by placing a heavily infested leaf from the main aphid colony on top of each cotyledon. Aphids were allowed to transfer overnight to accomplish an infestation of 80-100 aphids per plant and the host leaf was removed. The infested plants were then sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood, removed from the sprayer, and then maintained in a growth room under fluorescent lighting in a 24-hr photoperiod at 25°C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on untreated control plants, was determined after 5 days.

In this test, the compounds C-1, C-2, and C-3 respectively at 10 ppm showed at least 75% mortality in comparison with untreated controls.

B.3 Silverleaf whitefly (Bemisia argentifolii, adult)

The active compounds were formulated in cyclohexanone as a 10,0000 ppm solution supplied in 1.3 ml ABgene® tubes. These tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone: 50% water (v/v). A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v).

Cotton plants at the cotyledon stage (one plant per pot) were sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer. Each pot was placed into a plastic cup and 10 to 12 whitefly adults (approximately 3-5 days old) were introduced. The insects were collected using an aspirator and 0.6 cm, nontoxic Tygon® tubing (R-3603) connected to a barrier pipette tip. The tip, containing the collected insects, was then gently inserted into the soil containing the treated plant, allowing insects to crawl out of the tip to reach the foliage for feeding. Cups were covered with a reusable screened lid (150-micron mesh polyester screen PeCap from Tetko, Inc.). Test plants were maintained in a growth room at 25°C and 20-40% relative humidity for 3 days, avoiding direct exposure to fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the cup. Mortality was assessed 3 days after treatment, compared to untreated control plants. In this test, the C-1, C-2, and C-3 respectively at 10 ppm showed at least 75% mortality in comparison with untreated controls.

B.4 Vetch aphid (Megoura viciae)

The active compounds were formulated in 1:3 (vol:vol) DMSO : water with different concentrations of formulated compounds.

Bean leaf disks were placed into microtiterplates filled with 0.8% agar-agar and 2.5 ppm OPUS™. The leaf disks were sprayed with 2.5 µl of the test solution and 5 to 8 adult aphids were placed into the microtiter plates which were then closed and kept at 23 ± 1 °C and 50 ± 5% relative humidity under fluorescent light for 6 days. Mortality was assessed on the basis of vital, reproduced aphids. Aphid mortality and fecundity was then visually assessed. In this test, the compounds C-1, C-2, C-3, C-4, C-5, C-6, C-7, C-8, C-9, C-10, C-11, C-12, C-13, C-14, and C-15 respectively at 2500 ppm showed at least 75% mortality in comparison with untreated controls.

B.5 Green peach aphid (Myzus persicae)

The active compounds were formulated in cyclohexanone as a 10,0000 ppm solution supplied in 1.3 ml ABgene® tubes. These tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone: 50% water (v/v). A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v).

Bell pepper plants at the first true-leaf stage were infested prior to treatment by placing heavily infested leaves from the main colony on top of the treatment plants. Aphids were allowed to transfer overnight to accomplish an infestation of 30-50 aphids per plant and the host leaves were removed. The infested plants were then sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood, removed, and then maintained in a growth room under fluorescent lighting in a 24 hour photoperiod at 25°C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on untreated control plants, was determined after 5 days.

In this test, compounds C-1, C-2, C-3, and C-4 respectively at 10 ppm showed at least 75% mortality in comparison with untreated controls.

B.6 Rice plant hopper (Nilaparvata lugens)

Rice seedlings were cleaned and washed 24 hours before spraying. The active compounds were formulated in 50:50 acetone: water and 0.1% vol/vol surfactant (EL 620) was added. Potted rice seedlings were sprayed with 5 ml test solution, air dried, placed in cages and inoculated with 10 adults. Treated rice plants were kept at 28-29°C and relative humidity of 50-60%. Percent mortality was recorded after 72 hours.

In this test, C-5 at 500 ppm showed 75% mortality in comparison with untreated controls.

B.7 Orchid thrips (Dichromothrips corbetti)

The active compounds were formulated as a 50:50 (vol:vol) acetone:water solution. Surfactant (Alkamuls EL 620) was added at the rate of 0.1% (vol/vol). Vanda orchids petals were cleaned, washed and air dried prior to spraying. Petals were dipped into the test solution for 3 seconds, air dried, placed inside a resealable plastic and inoculated with 20 adults. The treated petals were kept inside the holding room at 28-29 °C and relative humidity of 50-60%. Percent mortality was recorded after 72 hours.

In this test, compound C-3 at 500 ppm showed at least 75% mortality in comparison with untreated controls.

B.8 Rice green leafhopper (Nephotettix virescens)

Rice seedlings were cleaned and washed 24 hours before spraying. The active compounds were formulated in 50:50 acetone: water, and 0.1 % vol/vol surfactant (EL 620) was added. Potted rice seedlings were sprayed with 5 ml test solution, air dried, placed in cages and inoculated with 10 adults. Treated rice plants were kept at 28-29°C and relative humidity of 50-60%. Percent mortality was recorded after 72 hours.

In this test, compound C-12 at 500 ppm showed at least 75% mortality in comparison with untreated controls.

B.9 Control of Boll Weevil

For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of 24-well-microtiter plates containing an insect diet and 20-30 A. grandis eggs.

The compounds were formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 20µl, using a custom built micro atomizer, at two replications. After application, microtiter plates were incubated at 23 + 1°C, 50 + 5 % RH for 5 days. Egg and larval mortality was then visually assessed. In this test, compound C-12 at 2500 ppm showed at least 75% mortality in comparison with untreated controls.

 A pyrazole compound of formula I, wherein R1 is H, C1-C2-alkyl, or C1-C2-alkoxymethyl; R2 is CH3, CH2F, CHF2, or CF3; R3 is a monospiro or dispiro 5- to 10-membered carbo- or heterocycle, which may contain 1 or 2 heteroatom moieties selected from N-Rc, O, and S(O)k, with k being 0, 1, or 2, which carbo- or heterocycle is unsubstitued or may be substituted by 1, 2, 3, or 4 radicals Ra3; Ra1 is CN, NO2, C(O)NH2, C(S)NH2, C1-C2-alkylcarbonyloxy, C1-C4-alkoxy, C1-C2-haloalkoxy, C1-C2-alkyloxycarbonyl, or S(O)nRb; Ra2 is halogen or a group mentioned for Ra1; Ra3 is halogen, C1-C2-alkyl, C1-C2-haloalkyl, C1-C2-alkoxy-C1-C2-alkyl, C1-C2-alkyliden, =O, =S, =NRb, =NORb, =NSRb, or a group mentioned for Ra1; n is 0, 1, or 2; Rb is H, C1-C2-alkyl, C1-C2-haloalkyl, C3-C6-cycloalkyl, or C1-C4-alkoxy, Rc is H, C1-C2-alkyl, C1-C2-haloalkyl, C1-C2-alkylcarbonyl, or C1-C2-alkoxy-carbonyl; R4 is C1-C4-alkyl or C1-C4-haloalkyl; or R3 and R4 together with the carbon atom, to which they are attached, form a monospiro or dispiro 5- to 10-membered carbo- or heterocycle, which may contain 1 or 2 heteroa-tom moieties selected from N-Rc, O, and S(O)k, with k being 0 1 or 2, which carbo-or heterocycle is unsubstituted or may be substituted by 1, 2, 3 or 4 radicals Ra3*; Ra3* is CN, C1-C2-haloalkyl, C1-C2-alkoxy-C1-C2-alkyl, or C1-C2-alkyliden; R5 is H, CH3, CN, F, OCH3, SCH3, CF3, OCF3, or SCF3; and the stereoisomers, salts, tautomers and N-oxides thereof. The pyrazole compound of claim 1, wherein R3 is spiro[2.2]pentyl, which is unsubstituted or carries one or two radicals Ra3, or 7-dispiro[2.0.1.2]-heptyl which is unsubstituted or carries a radical Ra3, and especially a radical selected from the group consisting of spiro[2.2]pentyl, 2-methylene-spiro[2.2]pentyl, 1-cyano-spiro[2.2]pentyl, 1-(trifluoromethyl)-spiro[2.2]pentyl, 4-methyl-spiro[2.2]pentyl, 4,4-dimethyl-spiro[2.2]pentyl, 4-(methoxymethyl)-spiro[2.2]pentyl, 4-(trifluoromethyl)-spiro[2.2]pentyl, and 7-dispiro[2.0.1.2]-heptyl. The pyrazole compound of claim 1 or 2, where R4 is CH3, C2H5, CHF2 or CF3. A pyrazole compound of formula I as defined in claim 1,
wherein
R3 and R4 together with the carbon atom, to which they are attached, form a monospiro or dispiro 5- to 10-membered carbo- or heterocycle, which may contain 1 or 2 heteroatom moieties selected from N-Rc, O, and S(O)k, which carbo- or heterocycle is unsubstituted or may be substituted by 1, 2, 3 or 4 radicals Ra3*;
Ra3* is CN, C1-C2-haloalkyl, C1-C2-alkoxy-C1-C2-alkyl, or C1-C2-alkyliden. The pyrazole compound of claim 4, where R3 and R4 together with the carbon atom, to which they are attached, form a monospiro or dispiro 5- to 10-membered carbocycle which is unsubstituted or substituted by 1 or 2 radicals Ra3*. The pyrazole compound of claim 4, where R3 and R4 together with the carbon atom, to which they are attached, form spiro[2.2]pentyl, which is unsubstituted or carries a radical Ra3 or 7-dispiro[2.0.1.2]-heptyl which is unsubstituted or carries one or two radicals Ra3 and where spiro[2.2]pentyl, 2-methylene-spiro[2.2]pentyl, 4-methyl-spiro[2.2]pentyl, 4,4-dimethyl-spiro[2.2]pentyl, 4-(methoxymethyl)-spiro[2.2]pentyl, 4-(trifluoromethyl)-spiro[2.2]pentyl and 7-dispiro[2.0.1.2]-heptyl. The pyrazole compound of any of claims claim 1 to 6, where R1 is CH3, or C2H5. The pyrazole compound of any of claims 1 to 6, where R2 is CH3, CHF2, or CF3. A composition comprising a compound according to any one of claims 1 to 8 and at least one inert liquid and/or solid carrier. An agricultural composition for combating animal pests comprising a compound according to any one of claims 1 to 8 and at least one inert liquid and/or solid acceptable carrier and, if desired, at least one surfactant. A non-therapeutic method for combating or controlling invertebrate pests, which method comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of a compound according to any of claims 1 to 8. A method for protecting growing plants or plant propagation materials from attack or infestation by invertebrate pests, which method comprises contacting a plant, a plant propagation material or soil or water in which the plant is growing, with a pesticidally effective amount of a compound according to any of claims 1 to 8. Plant propagation material comprising a compound according to any of claims 1 to 8, in an amount of from 0.1 g to 10 kg per 100 kg of seed. A method for protection of plant propagation material comprising contacting the plant propagation material with a compound according to any of claims 1 to 8 in an amount of from 0.1 g to 10 kg per 100 kg of plant propagation material. The use of a compound according to any of claims 1 to 8 for protecting growing plants or plant propagation material from attack or infestation by invertebrate pests. Pyrazolverbindung der Formel I, worin R1 H, C1-C2-Alkyl oder C1-C2-Alkoxymethyl bedeutet; R2 CH3, CH2F, CHF2 oder CF3 bedeutet; R3 einen 5- bis 10-gliedrigen Monospiro- oder Dispiro-Carbo- oder Heterocyclus bedeutet, der 1 oder 2 Heteroatomreste ausgewählt aus N-Rc, 0 und S(O)k enthalten kann, wobei k 0, 1 oder 2 bedeutet, wobei der Carbo- oder Heterocyclus unsubstituiert ist oder durch 1, 2, 3 oder 4 Reste Ra3 substituiert sein kann; Ra1 CN, NO2, C(O)NH2, C(S)NH2, C1-C2-Alkylcarbonyloxy, C1-C4-Alkoxy, C1-C2-Halogenalkoxy, C1-C2-Alkyloxycarbonyl oder S(O)nRb bedeutet; Ra2 Halogen oder eine für Ra1 erwähnte Gruppe bedeutet; Ra3 Halogen, C1-C2-Alkyl, C1-C2-Halogenalkyl, C1-C2-Alkoxy-C1-C2-alkyl, C1-C2-Alkyliden, =O, =S, =NRb, =NORb, =NSRb oder eine für Ra1 angegebene Gruppe bedeutet; n 0, 1 oder 2 bedeutet; Rb H, C1-C2-Alkyl, C1-C2-Halogenalkyl, C3-C6-Cycloalkyl oder C1-C4-Alkoxy bedeutet, Rc H, C1-C2-Alkyl, C1-C2-Halogenalkyl, C1-C2-Alkylcarbonyl oder C1-C2-Alkoxycarbonyl bedeutet; R4 C1-C4-Alkyl oder C1-C4-Halogenalkyl bedeutet; oder R3 und R4 gemeinsam mit dem Kohlenstoffatom, an das sie gebunden sind, einen 5- bis 10-gliedrigen Monospiro- oder Dispiro-Carbo- oder Heterocyclus bilden, der 1 oder 2 Heteroatomreste ausgewählt aus N-Rc, 0 und S(O)k enthalten kann, wobei k 0, 1 oder 2 bedeutet, wobei der Carbo- oder Heterocyclus unsubstituiert ist oder durch 1, 2, 3 oder 4 Reste Ra3* substituiert sein kann; Ra3* CN, C1-C2-Halogenalkyl, C1-C2-Alkoxy-C1-C2-alkyl oder C1-C2-Alkyliden bedeutet; R5 H, CH3, CN, F, OCH3, SCH3, CF3, OCF3 oder SCF3 bedeutet; und
ihre Stereoisomere, Salze, Tautomere und N-Oxide. Pyrazolverbindung nach Anspruch 1, wobei R3 Spiro[2.2]pentyl, das unsubstituiert ist oder einen oder zwei Reste Ra3 trägt, oder 7-Dispiro[2.0.1.2]heptyl, das unsubstituiert oder einen Rest Ra3 trägt, und insbesondere einen Rest ausgewählt aus der Gruppe bestehend aus Spiro[2.2]pentyl, 2-Methylenspiro[2.2]pentyl, 1-Cyanospiro[2.2]pentyl, 1-(Trifluormethyl)spiro[2.2]pentyl, 4-Methylspiro[2.2]pentyl, 4,4-Dimethylspiro[2.2]pentyl, 4-(Methoxymethyl)spiro[2.2]pentyl, 4-(Trifluormethyl)spiro[2.2]pentyl und 7-Dispiro[2.0.1.2]heptyl, bedeutet. Pyrazolverbindung nach Anspruch 1 oder 2, wobei R4 CH3, C2H5, CHF2 oder CF3 bedeutet. Pyrazolverbindung der Formel I wie in Anspruch 1 definiert,
wobei
R3 und R4 gemeinsam mit dem Kohlenstoffatom, an das sie gebunden sind, einen 5- bis 10-gliedrigen Monospiro- oder Dispiro-Carbo- oder Heterocyclus bilden, der 1 oder 2 Heteroatomreste ausgewählt aus N-Rc, 0 und S(O)k enthalten kann, wobei der Carbo- oder Heterocyclus unsubstituiert ist oder durch 1, 2, 3 oder 4 Reste Ra3* substituiert sein kann; Ra3*
CN, C1-C2-Halogenalkyl, C1-C2-Alkoxy-C1-C2-alkyl oder C1-C2-Alkyliden bedeutet. Pyrazolverbindung nach Anspruch 4, wobei R3 und R4 gemeinsam mit dem Kohlenstoffatom, an das sie gebunden sind, einen 5- bis 10-gliedrigen Monospiro- oder Dispiro-Carbocyclus bilden, der unsubstituiert ist oder durch 1 oder 2 Reste Ra3* substituiert ist. Pyrazolverbindung nach Anspruch 4, wobei R3 und R4 gemeinsam mit dem Kohlenstoffatom, an das sie gebunden sind, Spiro[2.2]pentyl, das unsubstituiert ist oder einen Rest Ra3 trägt, oder 7-Dispiro[2.0.1.2]heptyl, das unsubstituiert ist oder einen oder zwei Reste Ra3 trägt, bilden und wobei Spiro[2.2]pentyl, 2-Methylenspiro[2.2]pentyl, 4-Methylspiro[2.2]pentyl, 4,4-Dimethyl-spiro[2.2]pentyl, 4-(Methoxymethyl)spiro[2.2]pentyl, 4-(Trifluormethyl)spiro[2.2]pentyl und 7-Dispiro[2.0.1.2]heptyl. Pyrazolverbindung nach einem der Ansprüche 1 bis 6, wobei R1 CH3 oder C2H5 bedeutet. Pyrazolverbindung nach einem der Ansprüche 1 bis 6, wobei R2 CH3, CHF2 oder CF3 bedeutet. Zusammensetzung, umfassend eine Verbindung nach einem der Ansprüche 1 bis 8 und mindestens einen inerten flüssigen und/oder festen Träger. Landwirtschaftliche Zusammensetzung zum Bekämpfen von tierischen Schädlingen, umfassend eine Verbindung nach einem der Ansprüche 1 bis 8 und mindestens einen inerten flüssigen und/oder festen Träger sowie falls erwünscht mindestens ein Tensid. Nichttherapeutisches Verfahren zum Bekämpfen oder Kontrollieren von wirbellosen Schädlingen, bei dem man den Schädling oder seine Nahrungsquelle, seinen Lebensraum oder seine Brutstätten mit einer pestizidwirksamen Menge einer Verbindung nach einem der Ansprüche 1 bis 8 in Kontakt bringt. Verfahren zum Schützen von wachsenden Pflanzen oder pflanzlichem Vermehrungsgut gegen Befall oder Verseuchung durch wirbellose Schädlinge, bei dem man eine Pflanze, ein pflanzliches Vermehrungsgut oder Boden oder Wasser, worin die Pflanze wächst, mit einer pestizidwirksamen Menge einer Verbindung nach einem der Ansprüche 1 bis 8 in Kontakt bringt. Pflanzliches Vermehrungsgut, umfassend eine Verbindung nach einem der Ansprüche 1 bis 8 in einer Menge von 0,1 g bis 10 kg pro 100 kg Saatgut. Verfahren zum Schützen von pflanzlichem Vermehrungsgut, bei dem man das pflanzliche Vermehrungsgut mit einer Verbindung nach einem der Ansprüche 1 bis 8 in einer Menge von 0,1 g bis 10 kg pro 100 kg pflanzlichem Vermehrungsgut in Kontakt bringt. Verwendung einer Verbindung nach einem der Ansprüche 1 bis 8 zum Schützen von wachsenden Pflanzen oder von pflanzlichem Vermehrungsgut gegen Befall oder Verseuchung durch wirbellose Schädlinge. Composé de pyrazole de formule I dans lequel R1 est H, C1-C2-alkyle, ou C1-C2-alcoxyméthyle ; R2 est CH3, CH2F, CHF2, ou CF3 ; R3 est un monospiro- ou dispiro- carbo- ou hétérocycle de 5 à 10 chaînons, pouvant contenir 1 ou 2 motifs d'hétéroatomes choisis parmi N-Rc, 0, et S(O)k, k valant 0, 1 ou 2, lequel carbo- ou hétérocycle est non substitué ou peut être substitué par 1, 2, 3 ou 4 radicaux Ra3 ; Ra1 est CN, NO2, C(O)NH2, C(S)NH2, C1-C2-alkylcarbonyloxy, C1-C4-alcoxy, C1-C2-halogénoalcoxy, C1-C2-alkyloxycarbonyle, ou S(O)nRb ; Ra2 est halogène ou un groupement mentionné pour Ra1 ; Ra3 est halogène, C1-C2-alkyle, C1-C2-halogénoalkyle, C1-C2-alcoxy-C1-C2-alkyle, C1-C2-alkylidène, =O, =S, =NRb, =NORb, =NSRb, ou un groupement mentionné pour Ra1 ; n vaut 0, 1, ou 2 ; Rb est H, C1-C2-alkyle, C1-C2-halogénoalkyle, C3-C6-cycloalkyle, ou C1-C4-alcoxy, Rc est H, C1-C2-alkyle, C1-C2-halogénoalkyle, C1-C2-alkylcarbonyle, ou C1-C2-alcoxycarbonyle ; R4 est C1-C4-alkyle ou C1-C4-halogénoalkyle ; ou R3 et R4, conjointement avec l'atome de carbone auquel ils sont fixés, forment un monospiro- ou dispiro-carbo- ou hétérocycle de 5 à 10 chaînons, pouvant contenir 1 ou 2 motifs d'hétéroatomes choisis parmi N-Rc, 0, et S(O)k, k valant 0, 1 ou 2, lequel carbo- ou hétérocycle est non substitué ou peut être substitué par 1, 2, 3 ou 4 radicaux Ra3* ; Ra3* est CN, C1-C2-halogénoalkyle, C1-C2-alcoxy-C1-C2-alkyle, ou C1-C2-alkylidène ; R5 est H, CH3, CN, F, OCH3, SCH3, CF3, OCF3, ou SCF3 ; et les stéréoisomères, sels, tautomères et N-oxydes de celui-ci. Composé de pyrazole selon la revendication 1, dans lequel R3 est spiro[2.2]pentyle, qui est non substitué ou porte un ou deux radicaux Ra3, ou 7-dispiro[2.0.1.2]-heptyle qui est non substitué ou porte un radical Ra3, et notamment un radical choisi dans le groupe constitué par spiro[2.2]pentyle, 2-méthylène-spiro[2.2]pentyle, 1-cyano-spiro[2.2]pentyle, 1-(trifluorométhyl)spiro[2.2]pentyle, 4-méthyl-spiro[2.2]pentyle, 4,4-diméthyl-spiro[2.2]pentyle, 4-(méthoxyméthyl)spiro[2.2]pentyle, 4-(trifluorométhyl)spiro[2.2]pentyle, et 7-dispiro-[2.0.1.2]-heptyle. Composé de pyrazole selon la revendication 1 ou 2, dans lequel R4 est CH3, C2H5, CHF2 ou CF3. Composé de pyrazole de formule I tel que défini selon la revendication 1, dans lequel R3 et R4, conjointement avec l'atome de carbone auquel ils sont fixés, forment un monospiro- ou dispiro- carbo- ou hétérocycle de 5 à 10 chaînons, pouvant contenir 1 ou 2 motifs d'hétéroatomes choisis parmi N-Rc, 0, et S(O)k, lequel carbo- ou hétérocycle est non substitué ou peut être substitué par 1, 2, 3 ou 4 radicaux Ra3* ;
Ra3* est CN, C1-C2-halogénoalkyle, C1-C2-alcoxy-C1-C2-alkyle, ou C1-C2-alkylidène. Composé de pyrazole selon la revendication 4, dans lequel R3 et R4, conjointement avec l'atome de carbone auquel ils sont fixés, forment un monospiro- ou dispiro- carbocycle de 5 à 10 chaînons qui est non substitué ou substitué par 1 ou 2 radicaux Ra3*. Composé de pyrazole selon la revendication 4, dans lequel R3 et R4, conjointement avec l'atome de carbone auquel ils sont fixés, forment spiro[2.2]pentyle, qui est non substitué ou porte un radical Ra3 ou 7-dispiro-[2.0.1.2]heptyle qui est non substitué ou porte un ou deux radicaux Ra3 et où spiro[2.2]pentyle, 2-méthylène-spiro[2.2]pentyle, 4-méthyl-spiro[2.2]pentyle, 4,4-diméthyl-spiro[2.2]pentyle, 4-(méthoxyméthyl)spiro-[2.2]pentyle, 4-(trifluorométhyl)spiro[2.2]pentyle et 7-dispiro[2.0.1.2]-heptyle. Composé de pyrazole selon l'une quelconque des revendications 1 à 6, dans lequel R1 est CH3, ou C2H5. Composé de pyrazole selon l'une quelconque des revendications 1 à 6, dans lequel R2 est CH3, CHF2, ou CF3 . Composition comprenant un composé selon l'une quelconque des revendications 1 à 8, et au moins un véhicule inerte liquide et/ou solide. Composition agricole destinée à lutter contre des animaux nuisibles, comprenant un composé selon l'une quelconque des revendications 1 à 8 et au moins un véhicule inerte liquide et/ou solide et, si on le souhaite, au moins un agent tensioactif. Méthode non thérapeutique destinée à lutter contre ou contrôler des invertébrés nuisibles, laquelle méthode comprend la mise en contact dudit nuisible ou de sa source d'alimentation, son habitat ou ses lieux de reproduction, avec une quantité efficace sur le plan pesticide d'un composé selon l'une quelconque des revendications 1 à 8. Méthode destinée à protéger des plantes en croissance ou des matériels de propagation végétaux contre une attaque ou une infestation par des invertébrés nuisibles, laquelle méthode comprend la mise en contact d'une plante, d'un matériel de propagation végétal ou du sol ou de l'eau où la plante se développe, avec une quantité efficace sur le plan pesticide d'un composé selon l'une quelconque des revendications 1 à 8. Matériel de propagation végétal comprenant un composé selon l'une quelconque des revendications 1 à 8, selon une quantité allant de 0,1 g à 10 kg pour 100 kg de semences. Méthode destinée à protéger un matériel de propagation végétal, comprenant la mise en contact du matériel de propagation végétal avec un composé selon l'une quelconque des revendications 1 à 8, selon une quantité allant de 0,1 g à 10 kg pour 100 kg de matériel de propagation végétal. Utilisation d'un composé selon l'une quelconque des revendications 1 à 8, pour la protection de plantes en croissance ou d'un matériel de propagation végétal contre une attaque ou une infestation par des invertébrés nuisibles. REFERENCES CITED IN THE DESCRIPTION

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Non-patent literature cited in the description